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(12) Patent Application Publication (10) Pub. No.: US 2003/0207962 A1 Oya Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2003/0207962 A1 Oya Et Al US 20030207962A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0207962 A1 Oya et al. (43) Pub. Date: Nov. 6, 2003 (54) ANTIFOULING COATING COMPOSITION, (57) ABSTRACT COATING FILM THEREFROM, BASE MATERIAL COVERED WITH THE COATING FILM AND ANTIFOULING METHOD An antifouling coating composition comprising (A) a silyl ester copolymer containing constituent units derived from a (76) Inventors: Masaaki Oya, Ohtake-shi (JP); Naoya polymerizable unsaturated carboxylic acid silyl ester; (B) a Nakamura, Ohtake-shi (JP); Makoto carboxylic acid, (C) a bivalent or trivalent metal compound; Tsuboi, Ohtake-shi (JP) and (D) a dehydrating agent. It is preferred that the com ponent (C) be contained in an amount of 1.2 equivalents or Correspondence Address: more, in terms of the number of equivalents of metal as a Leonard W. Sherman constituent of the component (C), per equivalent of carboxyl Sherman & Shalloway group of the carboxylic acid (B); that the component (C) be 413 N. Washington Street a bivalent metal compound; and that the component (C) be Alexandria, VA 22314 (US) a compound of at least one metal Selected from the group consisting of Zinc, copper, magnesium, calcium and barium. (21) Appl. No.: 10/375,005 From the antifouling coating composition, there can be obtained an antifouling coating film which exhibits leSS (22) Filed: Feb. 28, 2003 cracking tendency, excellent adherence So as to ensure leSS (30) Foreign Application Priority Data peeling tendency and desirably controlled hydrolysis rate So as to be excellent in antifouling performance, in particular, Mar. 6, 2002 (JP)......................................... 2002-60696 antifouling properties in highly fouling environment and long-term antifouling properties. With respect to the pro Publication Classification Vided antifouling coating composition, its Storage Stability is high, its concentration can be increased, the amount of (51) Int. Cl. ................................ B05D 3/02; CO8K 3/00 Solvent used therefor can be reduced, and its applicability is (52) U.S. Cl. ....................... 523/177; 427/385.5; 523/122 high. US 2003/0207962 A1 Nov. 6, 2003 ANTIFOULING COATING COMPOSITION, and tributyltin halides (BuSnX wherein X is a halogen COATING FILM THEREFROM, BASE MATERIAL atom), So that an antifouling effect is exerted. Furthermore, COVERED WITH THE COATING FILM AND the copolymer hydrolyzate per se is a “hydrolyzable self ANTIFOULING METHOD polishing paint' which is rendered water-Soluble and thus is dissolved in the Seawater, So that no resin residue is left on FIELD OF THE INVENTION the surface of the ship bottom coating with the result that 0001. The present invention relates to an antifouling always an active Surface can be maintained. coating composition which contains a silyl ester copolymer, 0006. However, the above organotin compounds are so an antifouling coating film formed from the antifouling highly toxic that apprehensions are being entertained with coating composition, an antifouling method wherein the respect to marine pollution, occurrence of anomalous fish antifouling coating composition is used, and a marine vessel and anomalous shellfish and adverse effects on ecosystem (hull) or underwater structure covered with the coating film. through food chain. Therefore, the development of a non 0002 More particularly, the present invention relates to Stannic antifouling paint is desired as a Substitute therefor. an antifouling coating composition which can be formed 0007 For example, antifouling paints based on silyl into an antifouling paint whose Storage Stability is excellent esters as described in Japanese Patent Laid-open Publication and wherein the amount of Solvent used can be reduced due Nos. 4(1992)-264170 (reference (a)), 4(1992)-264169 (ref to low Viscosity. From the antifouling paint, there can be erence (b)) and 4(1992)-264168 (reference (c)) can be obtained an antifouling coating film which exhibits leSS mentioned as the above nonstannic antifouling paint. How cracking tendency, excellent adherence So as to ensure leSS ever, these antifouling paints have Such problems that not peeling tendency and desirably controlled hydrolysis rate So only are their antifouling capabilities poor but also cracking as to be excellent in antifouling performance (antifouling and peeling are likely to occur as pointed out in Japanese activity), in particular, antifouling properties in Stationary Patent Laid-open Publication Nos. 6(1994)-157941 (refer environment or highly fouling environment and long-term ence (d)) and 6(1994)-157940 (reference (e)). antifouling properties. Further, the present invention relates 0008 Further, Japanese Patent Laid-open Publication to an antifouling coating film formed from the antifouling No. 2(1990)-196869 (reference (f)) teaches, for example, an coating composition, an antifouling method wherein the antifouling paint comprising a blocked acid-functionality antifouling coating composition is used, and a hull or copolymer (A) which is obtained by copolymerizing trim underwater Structure covered with the coating film. ethylsilyl methacrylate, ethyl methacrylate and methoxy ethyl acrylate in the presence of an azo polymerization BACKGROUND OF THE INVENTION initiator and which contains a triorganosilyl carboxylate 0.003 Ship bottoms, underwater structures, fishing nets ester group, namely, a carboxylic acid group blocked with a and the like are likely to have their appearance and function trimethylsilyl group; a polycationic compound (B) which is damaged by the adhesion to Surface and propagation of an organic-Solvent-Soluble Salt of polyvalent metal; and a various aquatic organisms including animals. Such as Shell biocide. In the use of this antifouling paint, for example, the fishes, hard-shelled mussels and barnacles, plants Such as trimethylsilyl group blocking the carboxylic acid group is laver (Seaweeds) and bacteria which is caused when they are Split off by water contained in the paint, and the polyvalent exposed to water for a prolonged period of time. cation reacts with thus formed carboxylic acid group of the acid-functionality copolymer (A), thereby effecting a 0004. In particular, when such an aquatic organism crosslinking and hardening. However, in this reference, adheres to a ship's bottom and propagates, it may occur that there is no description with respect to a method of coping the Surface roughness of the ship as a whole is increased to with water produced by, for example, adding a carboxylic thereby lower the speed of the ship and increase the fuel acid and Zinc white (Zinc oxide) to the paint. Further, the consumed by the ship. Removing the aquatic organism from antifouling paint poses Such a problem that when a free acid the ship bottom necessitates Spending of extensive labor and remains in the antifouling paint, the antifouling paint loaded working time. Also, when bacteria adhere to, for example, with a component which reacts with a free acid to thereby an underwater Structure and propagate and, further, Slime produce water, there occur, for example, gelation and thick (sludgy matter) adheres thereto to cause putrefaction, or ening causing deterioration of Storage Stability, deterioration when a large Sticky organism adheres to the Surface of an of performance, etc. Still further, there is such a problem that underwater Structure, for example, Steel Structure and propa when the acid-functionality copolymer (A) is hydrolyzed gates to thereby damage the coating for corrosion prevention and when a crosslinking reaction occurs between thus provided on the underwater Structure, there is the danger that formed acid group and the polycation, the elution (leaching) damageS Such as deterioration of the Strength and function of of the acid-functionality copolymer (A) would be Sup the underwater Structure and thus marked Shortening of the pressed to result in deterioration of the abradability of life thereof are invited. coating film and deterioration of long-term antifouling capa 0005. It is common practice to apply, for example, a bility. composition comprising a copolymer of tributyltin meth acrylate and methyl methacrylate or the like and cuprous 0009 Thus, the antifouling paint described in the above oxide (Cu2O) as an antifouling paint having excellent anti reference has poor Storage Stability, and the coating film fouling properties to Ship bottoms, etc. So as to avoid the obtained from the antifouling paint has a drawback in that above damages. This copolymer of the antifouling paint is the cracking resistance thereof is not fully Satisfactory. hydrolyzed in the Seawater to thereby liberate organotin 0010) Published Japanese Translation of PCT Patent compounds such as bistributyltin oxide (tributyltin ether of Applications from Other States, No. 60(1985)-500452 (ref the formula BuSn-O-SnBu wherein Bu is a butyl group) erence (g)) and Japanese Patent Laid-open Publication No. US 2003/0207962 A1 Nov. 6, 2003 63(1988)-215780 describe a resin for antifouling paint 0014) wherein each of R to R represents the same which is obtained by copolymerizing a vinyl monomer group as represented by R' to R or a group of the having an organosilyl group, Such as a trialkylsilyl ester of formula (b), (meth)acrylic acid, with another vinyl monomer and which has a number average molecular weight of 3000 to 40,000. 0015) provided that m groups represented by R and It is further described that the resin can be blended with an R may be identical with or different from each organic water coupler Such
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